CN107667122A - The method for aoxidizing the material based on starch - Google Patents
The method for aoxidizing the material based on starch Download PDFInfo
- Publication number
- CN107667122A CN107667122A CN201680031137.0A CN201680031137A CN107667122A CN 107667122 A CN107667122 A CN 107667122A CN 201680031137 A CN201680031137 A CN 201680031137A CN 107667122 A CN107667122 A CN 107667122A
- Authority
- CN
- China
- Prior art keywords
- tubular body
- reactor
- rotor
- starch
- pulverulent material
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 94
- 229920002472 Starch Polymers 0.000 title claims abstract description 77
- 235000019698 starch Nutrition 0.000 title claims abstract description 77
- 239000008107 starch Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 60
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 66
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000001238 wet grinding Methods 0.000 claims abstract description 45
- 238000007599 discharging Methods 0.000 claims abstract description 43
- 239000001254 oxidized starch Substances 0.000 claims abstract description 40
- 235000013808 oxidized starch Nutrition 0.000 claims abstract description 40
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 22
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 21
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 239000002826 coolant Substances 0.000 claims description 12
- 241000209140 Triticum Species 0.000 claims description 11
- 235000021307 Triticum Nutrition 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000008676 import Effects 0.000 claims description 11
- 235000013339 cereals Nutrition 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 9
- 240000007594 Oryza sativa Species 0.000 claims description 8
- 235000007164 Oryza sativa Nutrition 0.000 claims description 8
- 240000008042 Zea mays Species 0.000 claims description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 235000005822 corn Nutrition 0.000 claims description 8
- 235000009566 rice Nutrition 0.000 claims description 8
- 244000068988 Glycine max Species 0.000 claims description 7
- 235000010469 Glycine max Nutrition 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 244000061456 Solanum tuberosum Species 0.000 claims description 5
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 240000001592 Amaranthus caudatus Species 0.000 claims description 4
- 235000009328 Amaranthus caudatus Nutrition 0.000 claims description 4
- 244000075850 Avena orientalis Species 0.000 claims description 4
- 235000007319 Avena orientalis Nutrition 0.000 claims description 4
- 235000007558 Avena sp Nutrition 0.000 claims description 4
- 240000006162 Chenopodium quinoa Species 0.000 claims description 4
- 102100028717 Cytosolic 5'-nucleotidase 3A Human genes 0.000 claims description 4
- 240000008620 Fagopyrum esculentum Species 0.000 claims description 4
- 235000009419 Fagopyrum esculentum Nutrition 0.000 claims description 4
- 240000005979 Hordeum vulgare Species 0.000 claims description 4
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 241000219745 Lupinus Species 0.000 claims description 4
- 240000003183 Manihot esculenta Species 0.000 claims description 4
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 4
- 240000004713 Pisum sativum Species 0.000 claims description 4
- 235000010582 Pisum sativum Nutrition 0.000 claims description 4
- 235000012735 amaranth Nutrition 0.000 claims description 4
- 239000004178 amaranth Substances 0.000 claims description 4
- 235000005489 dwarf bean Nutrition 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 4
- 244000045195 Cicer arietinum Species 0.000 claims description 3
- 235000010523 Cicer arietinum Nutrition 0.000 claims description 3
- 244000082988 Secale cereale Species 0.000 claims description 3
- 235000007238 Secale cereale Nutrition 0.000 claims description 3
- 240000006677 Vicia faba Species 0.000 claims description 3
- 235000010749 Vicia faba Nutrition 0.000 claims description 3
- 235000002098 Vicia faba var. major Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 230000036760 body temperature Effects 0.000 claims 2
- 241000255789 Bombyx mori Species 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000001465 metallisation Methods 0.000 claims 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 10
- 229910000765 intermetallic Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 235000013312 flour Nutrition 0.000 description 7
- 235000013305 food Nutrition 0.000 description 7
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- 108010061711 Gliadin Proteins 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000009965 odorless effect Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 208000015943 Coeliac disease Diseases 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 108010068370 Glutens Proteins 0.000 description 1
- 235000019759 Maize starch Nutrition 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YTAHJIFKAKIKAV-XNMGPUDCSA-N [(1R)-3-morpholin-4-yl-1-phenylpropyl] N-[(3S)-2-oxo-5-phenyl-1,3-dihydro-1,4-benzodiazepin-3-yl]carbamate Chemical compound O=C1[C@H](N=C(C2=C(N1)C=CC=C2)C1=CC=CC=C1)NC(O[C@H](CCN1CCOCC1)C1=CC=CC=C1)=O YTAHJIFKAKIKAV-XNMGPUDCSA-N 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000021312 gluten Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 210000002221 olecranon process Anatomy 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000002415 sodium dodecyl sulfate polyacrylamide gel electrophoresis Methods 0.000 description 1
- 235000019605 sweet taste sensations Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229960005196 titanium dioxide Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1812—Tubular reactors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/005—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the outlet side being of particular interest
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00743—Feeding or discharging of solids
- B01J2208/00752—Feeding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/06—Details of tube reactors containing solid particles
- B01J2208/065—Heating or cooling the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
- B01J2219/00085—Plates; Jackets; Cylinders
Abstract
A kind of method for being used to aoxidize the pulverulent material containing starch, it includes following step one by one：By the pulverulent material containing starch and hydrogen peroxide (H2O2) aqueous solution mixing, and add ammonia spirit in the resulting mixture and it is reacted with the mixture；The step of this method can also include said mixture is further dried to obtain the pulverulent material containing oxidized starch；This method can advantageously comprise following steps：The continuous stream supply of pulverulent material containing starch is included into the first reactor (R) of cylinder tubular body (1) and rotor, the rotor is arranged in cylinder tubular body, it includes being provided with the axle (8) for being radially therefrom prominent element (9), and rotated with the speed more than or equal to 50rpm, the continuous stream of aqueous hydrogen peroxide solution is supplied into the reactor；The continuous stream and hydroperoxidation of pulverulent material containing starch；The continuous stream of wet powder is discharged from the discharging opening (7) of first reactor, and continuous stream supply is included into cylindrical tubular body (101) and the second reactor (R') of rotor, the rotor is arranged in cylinder tubular body, it includes being provided with the axle (108) for being radially therefrom prominent element (109), and is rotated with the speed more than or equal to 50rpm；By the continuous stream supply second reactor (R') of ammonia spirit；The continuous stream of the wet-milling containing oxidized starch is discharged from the discharging opening (107) of second reactor；Wet-milling drying to water content is less than or equal to 20 weight %, so as to obtain the pulverulent material containing oxidized starch.
Description
Technical field
The present invention relates to a kind of method for aoxidizing the material based on starch, particularly aoxidize what is obtained from cereal and starch
The method of coarse powder.
Background technology
Oxidized starch is used to need all industrial circles with good filming and the additive of cohesive.
In the food industry, oxidized starch is a kind of thickener, it is allowed to which (E-1404) is for example in cream, tartar sauce and sweet taste
Used in product, and in paper industry, it is used as improving the additive of paper strength, for improving its printing performance and changing
The retention of kind cationic additive, and the adhesive as paper-making fibre.WO 00/15670 is described using oxidized starch
Adhesive as coating.
By oxidation, the viscosity of starch reduces in solution or dispersion liquid, and the mean molecule quantity of starch reduces.
The oxidation of starch is carried out as oxidant usually using alkaline hypochlorite or peroxide.
For example it is described using the oxidation of alkaline hypochlorite in WO 03/018638 is applied for.
Using peroxide such as hydrogen peroxide (oxidized water) oxidation generally with metallic catalyst such as cupric,
Ferrous iron or manganese are carried out together.
Such as described in WO 00/15670 is applied for using hydrogen peroxide and Cu2+Oxidation.
These known methods in the case of using alkaline hypochlorite have niff in final product be present
The shortcomings that with alkali metal salt residue, and in the case where using cupric or iron compound, there is the whiteness for reducing starch
The shortcomings that with copper and molysite residue be present.This makes the oxidized starch of acquisition not be suitable for grocery trade (alimentary) or system
Medicine company.
In view of the foregoing, problem of the invention is that providing a kind of method for producing oxidized starch, this method will not be led
There is niff or metallic compound residue in cause, metallic compound residue can cause starch gelatinization in oxidized starch
Or the loss of its quaternized property, and especially, this method is not related to related to the reagent used at present to operating personnel
Health caused by any risk.
According to another aspect of the present invention, the present invention relates to a kind of oxygen for the material based on starch being made up of meals
Change method.
In this respect, WO 2014/027139, which is disclosed, a kind of is containing Cu2+Or Fe2+Catalyst in the presence of be used for
The method for aoxidizing the Starch Fraction of cereal, its object is to reduce the gluten content for including proline, the thus starch portion of cereal
Lease making is acted on by oxidant, and the oxidant is selected from hydrogen peroxide, ascorbic acid and titanium oxide.
In this case, the color for changing coarse powder in the final product be present and used for human or animal's food
Product in be the shortcomings that undesirable metallic compound is persistently present.
The content of the invention
According to the present invention, pass through material of the oxidation containing starch carried out in the case of in the absence of any metallic compound
Method solve above mentioned problem, and this method includes following step one by one：
A) pulverulent material containing starch is provided；
B) by the pulverulent material and aqueous hydrogen peroxide solution (H2O2) mixing；And
C) ammonia spirit (aqueous solution of ammonia) is added into thus obtained mixture and makes it
Reacted with the mixture.
Step can be finally dried in final mixture, to obtain the pulverulent material containing oxidized starch.
The above-mentioned pulverulent material containing starch be selected from include separate sources (such as from corn, potato, wheat, cassava,
Rice and beans) starch composition group, the coarse powder from cereal, wherein cereal particularly wheat, rice, corn, barley, black
Wheat, oat, buckwheat, three-coloured amaranth and quinoa, and the coarse powder from beans, wherein beans particularly beans (beans), pea, olecranon
Beans, broad bean, French beans, lupin, chickling and soybean (soybeans).
Reaction is generally carried out at room temperature, is carried out preferably at a temperature of 15 to 25 DEG C.
The w/v concentration of above-mentioned aqueous hydrogen peroxide solution is preferably between 5% to 20%.
The w/v concentration of above-mentioned ammonia spirit is preferably between 5% to 20%.Pulverulent material and peroxide containing starch
Change the weight ratio between aqueous solution of hydrogen generally between 3 to 20.
Weight between aqueous hydrogen peroxide solution and ammonia spirit is than usually 1 to 10.
The method according to the invention, the water content of the pulverulent material containing oxidized starch obtained at the end of reaction are preferred
It is less than by above-mentioned drying steps or the 20 weight % equal to pulverulent material gross weight, preferably 5 to 15 weight %.
The reaction of the method according to the invention preferably makes the aqueous solution of the pulverulent material containing starch and reagent closely connect
Carried out in tactile reactor.
Reactor especially suitable for implementing the inventive method is made up of such reactor, and the reactor includes having water
The cylinder tubular body of flat axis, its have it is at least one be used for introduce reagent opening and it is at least one be used for discharge final production
The opening of product；Optionally with making the temperature of the tubular body reach the heating or cooling jackets of predetermined temperature；And rotor, its
It is arranged in cylinder tubular body and the axle of prominent element is radially therefrom including being provided with.
When using this device, according to the first embodiment of the invention, the side of the pulverulent material containing starch is aoxidized
Method comprises the following steps：
A) continuous stream of pulverulent material containing starch supplies to the first reactor of types described above, wherein rotor with
Speed rotation more than or equal to 50rpm, the material is dispersed into by the continuous stream of the pulverulent material containing starch
Particle stream；
B) continuous stream of aqueous hydrogen peroxide solution supplies described together with the continuous stream of the pulverulent material containing starch
Reactor, the continuous stream of the aqueous hydrogen peroxide solution are dispersed into fine droplet stream by above-mentioned rotor；
C) particle and drop centrifugation are leaned against into the inwall of the first reactor, formed high turbulence, dynamic,
Thin tubular fluid layer, wherein the drop of the particle of the pulverulent material containing starch and the aqueous hydrogen peroxide solution pass through it is described
The radially projecting element of rotor keeps mechanically being in close contact, while with the contiguously direction substantially of the inwall with reactor
Discharging opening promotes；
D) when promoting the inwall for generally contacting turbo-reactor towards discharging opening, the pulverulent material containing starch
Reacted with hydrogen peroxide in the thin layer；
E) from the continuous stream of discharging opening discharge wet-milling and the continuous stream is supplied into the second anti-of types described above
Device is answered, wherein rotor is rotated with the speed more than or equal to 50rpm；
F) continuous stream of ammonia spirit supplies the second reactor together with the continuous stream of the wet-milling, ammonia spirit
Continuous stream is dispersed into fine droplet stream by above-mentioned rotor；
G) continuous flow centrifugation is made to lean against described second by the effect of the radially projecting element of the rotor
The inwall of reactor so that they are contacted towards discharging opening and moved substantially with the inwall with the second reactor；
H) from the continuous stream of wet-milling of the discharging opening discharge containing oxidized starch；
I) the wet-milling drying to water content is less than or equal to 20 weight %, so as to obtain the powdery containing oxidized starch
Material.
The temperature of the inwall of above-mentioned first reactor preferably remains in room temperature, eligibly at 15-25 DEG C.
The temperature of the inwall of above-mentioned second reactor preferably remains in room temperature, eligibly at 15-25 DEG C.
The w/v concentration of above-mentioned aqueous hydrogen peroxide solution is preferably between 5% to 20%.
The w/v concentration of above-mentioned ammonia spirit is between 5% to 20%.
Supply the powder containing starch in the flow and supplied reactor of the aqueous hydrogen peroxide solution stream in first reactor
Ratio between the flow of shape material stream is preferably between 1:20 to 1:Between 5, eligibly between 1:15 to 1:Between 8.
Supply the flow of the flow and the wet-milling material stream from first reactor discharge of the ammonia spirit stream of second reactor
Between ratio be preferably between 1:20 to 1:Between 5, eligibly between 1:15 to 1:Between 8.
Residence time of the pulverulent material containing starch in first reactor generally between 30 seconds to 20 minutes, this
Depending on the degree of oxidation to be obtained, this increase with the residence time and increase.
Residence time of the wet-milling in second reactor is generally between 30 seconds to 5 minutes.
The rotary speed of rotor is preferably between 50 between 1500rpm, advantageously between 150 between 500rpm.
The said elements protruded from the Axial and radial of first reactor and the rotor of second reactor may each be such as bar, leaf
The form of piece, V-arrangement blade or agitator (beater).
According to alternate embodiments, using reactor, wherein the reactor includes the cylinder tubulose with horizontal axis
Main body, the first opening and second for being used to introduce reagent for being provided with the adjacent one end for being arranged in the cylinder tubular body are opened
Mouthful, the position being disposed between the first end of the cylinder tubular body and the opposite end of the cylinder tubular body
For introducing the 3rd opening of reagent, and at least one opening for being used to discharge final products；Optionally with making the pipe
The temperature of shape main body reaches the heating or cooling jackets of predetermined temperature；And rotor, it is arranged in cylinder tubular body and wrapped
Include the axle for being provided with and being radially therefrom prominent element.
When using the reactor, the method for aoxidizing the pulverulent material containing starch comprises the following steps：
A') continuous stream of pulverulent material containing starch is supplied to the reaction of types described above by first import
Device, rotor are rotated with the speed more than or equal to 50rpm, and the continuous stream of the pulverulent material containing starch is dispersed into institute
State the particle stream of material；
B' the continuous stream of aqueous hydrogen peroxide solution) is supplied by the reactor, the peroxidating by second import
The continuous stream of aqueous solution of hydrogen is dispersed into fine droplet stream by above-mentioned rotor；
C' the particle and drop centrifugation) are leaned against into the inwall of the reactor, form high turbulence, dynamic, thin
Tubular fluid layer, wherein the drop of the particle of the pulverulent material containing starch and the aqueous hydrogen peroxide solution passes through described turn
The radially projecting element of son keeps mechanically being in close contact, while contiguously direction goes out substantially with the inwall with reactor
Material mouth promotes；
D') when promoting the generally inwall of contact reactor towards discharging opening, the pulverulent material containing starch is made
Interacted with hydrogen peroxide in the thin layer；
E') continuous stream of ammonia spirit is sent into the reactor by the triple feed inlet, ammonia spirit it is continuous
Stream is dispersed into fine droplet stream by above-mentioned rotor；
F') continuous flow centrifugation is made to lean against the reaction by the action of the radially projecting element of the rotor
The inwall of device so that they are contiguously moved towards discharging opening substantially with the inwall with the reactor；
G') from the continuous stream of wet-milling of the discharging opening discharge containing oxidized starch；
H' the wet-milling drying to water content) is less than or equal to 20 weight %, so as to obtain the powder containing oxidized starch
Shape material.
Preferably, length approximately half distance of above-mentioned 3rd opening along above-mentioned cylinder tubular body is arranged.
The w/v concentration of above-mentioned aqueous hydrogen peroxide solution is preferably between 5% to 20%.
The w/v concentration of above-mentioned ammonia spirit is preferably between 5% to 20%.
The flow of the aqueous hydrogen peroxide solution stream of supplied reactor and the pulverulent material stream containing starch of supplied reactor
Flow between ratio be preferably between 1:20 to 1:Between 5, eligibly between 1:15 to 1:Between 8.
The flow of the flow of the ammonia spirit stream of supplied reactor and the pulverulent material stream containing starch of supplied reactor
Between ratio be preferably between 1:20 to 1:Between 5, eligibly between 1:15 to 1:Between 8.
Residence time of the pulverulent material containing starch in reactor, this depended on generally between 30 seconds to 20 minutes
In the degree of oxidation to be obtained, its increase with the residence time and increase.
The rotary speed of rotor is preferably between 50 between 1500rpm, advantageously between 150 between 500rpm.
The said elements protruded from the Axial and radial of rotor can be the form of such as bar, blade, V-arrangement blade or agitator.
In above-mentioned two embodiment, reaction includes soaking the pulverulent material containing starch and aqueous hydrogen peroxide solution
First stage together, then the pulverulent material soaked through hydrogen peroxide and ammonia spirit are reacted and activate the oxygen of starch chain
Change reaction.
Preferably, the above-mentioned steps i) and h' of wet-milling are dried by turbo dryer), the turbo dryer includes
Cylinder tubular body with horizontal axis, it is provided with least one charging aperture and at least one discharging opening；It is described for making
The temperature of tubular body reaches the heating mantle of predetermined temperature；And rotor, it is arranged in cylinder tubular body and including having
It is radially therefrom the axle of prominent element.
Using the turbo dryer, step i) and h' is dried)：
J) by least one charging aperture, the wet-milling discharged from the reactor is supplied into the turbine and dried
Device, the inwall of turbo dryer is maintained at least 70 DEG C of temperature by the heating mantle, and rotor is with least 150rpm's
Speed rotates；
L) centrifuge and the wet-milling is promoted by the action of the rotor in turbo dryer；And
M) from the discharging opening of turbo dryer discharge with water content less than or equal to 20 weight % containing oxidized starch
The continuous stream of pulverulent material.
Alternatively, with above-mentioned wet-milling stream is supplied into turbo dryer according to step j) while, at least 50 DEG C are heated to
The gas stream (preferably air stream) of temperature is also fed in the turbo dryer by above-mentioned at least one charging aperture.
The temperature of the inwall of turbo dryer preferably remains in 70-180 DEG C, eligibly at 130-150 DEG C.
The rotary speed of the rotor of turbo dryer is preferably set to 300-1200rpm.
The said elements protruded from the Axial and radial of rotor can be the form of such as bar, blade, V-arrangement blade or agitator.
The temperature for supplying the air-flow of turbo dryer is preferably between 50 DEG C to 250 DEG C, between 120 DEG C extremely eligibly
Between 150 DEG C.
Residence time of the above-mentioned wet-milling in turbo dryer, this depended on containing generally between 30 seconds to 20 minutes
The degree of drying for the oxidized starch to be obtained, its increase with the residence time and increase.
According to its another aspect, it is used for implementation setting according to the method for above-mentioned first embodiment the present invention relates to a kind of
Standby, it includes：
First reactor, including the cylinder tubular body with horizontal axis, have at least one for introducing reagent
Opening and at least one opening for being used to discharge final products；Optionally with making the temperature of the tubular body reach pre- constant temperature
The heating mantle or coolant jacket of degree；And rotor, its be arranged in cylinder tubular body and including be provided be radially therefrom it is prominent
The axle of element；
Second reactor, including the cylinder tubular body with horizontal axis, have at least one for introducing reagent
Opening and at least one opening for being used to discharge final products；Optionally with making the temperature of the tubular body reach pre- constant temperature
The heating mantle or coolant jacket of degree；And rotor, its be arranged in cylinder tubular body and including be provided be radially therefrom it is prominent
The axle of element.
The equipment may further include turbo dryer, and the turbo dryer includes the cylinder tubulose with horizontal axis
Main body, it has at least one charging aperture and at least one discharging opening；Heating mantle；And rotor, it is arranged in cylinder tubulose master
The axle of prominent element is radially therefrom in body and including being provided with.
In addition, the equipment can also include：
Injection device with tubular body, it is provided with import, at least one discharging opening stream with first reactor
Body connects, and outlet, is fluidly connected with least one charging aperture of second reactor；The blade being supported in tubular body
Or screw rotor.
Injection device with tubular body, it is provided with import, at least one discharging opening stream with second reactor
Body connects, and outlet, is fluidly connected with least one charging aperture of turbo dryer；The blade being supported in tubular body
Or screw rotor.
According on the other hand, it is used for equipment of the implementation according to the method for above-mentioned alternate embodiments the present invention relates to a kind of,
It includes：
Including the cylinder tubular body with horizontal axis, its be provided be arranged in the cylinder tubular body one end it is attached
Near the first opening and the second opening that are used to introduce reagent, be disposed in the cylinder tubular body the first end and
Position between the opposite end of the cylinder tubular body is used for the 3rd opening for introducing reagent, and at least one for discharging
The opening of final products；Optional heating mantle or coolant jacket；And rotor, it is arranged in cylinder tubular body and including setting
There is the axle for being radially therefrom prominent element.
The equipment can also be included as implementing to be done according to the turbine described by the equipment of the method for first embodiment
Dry device.
In addition, the equipment can also include the injection device with tubular body, it is provided with import, with reactor
At least one discharging opening fluidly connects, and outlet, is fluidly connected with least one charging aperture of turbo dryer；It is supported on
Blade or screw rotor in tubular body.
According on the other hand, the present invention relates to a kind of pulverulent material containing oxidized starch, and it can be by as described above
Method by selected from by including：From corn, potato, wheat, cassava, rice and the starch of beans, come wheat, water freely
Rice, corn, barley, rye, oat, buckwheat, three-coloured amaranth and quinoa cereal coarse powder, and come freely beans (beans), pea,
Powder in the group that chick-pea, broad bean, French beans, lupin, chickling and the coarse powder of the beans of soybean (soybeans) are formed
Shape material and obtain.
When the pulverulent material containing starch is by Starch formation, the product obtained by the method for the present invention applies to
The oxidized starch of all purposes referred to further above, in view of the method according to the invention will not cause to exist in final products
The fact that any metallic compound residue, special recommendation are used for food and medicinal usage.In fact, excessive hydrogen peroxide is complete
Inactivated, then completely eliminated in subsequent drying steps any remaining in the wet-milling discharged from reactor by ammonia entirely
Ammonia.
The oxidized starch for handling the starch in any source by using the method according to the invention and obtaining is complete white
, and produce aqueous dispersion/solution that viscosity is significantly less than the solution/dispersion of the starting starch with same concentrations.
When the pulverulent material containing starch used in the method according to the invention is meals, such as wheat flour or thick
Therefore grain flour, method according to the invention it is possible to obtain the coarse powder of wherein seitan complete deactivation, and is also suitable for as with abdomen
It is prepared by the food of the people of chamber disease (coeliac disease) or seitan intolerance (gluten intolerance).At this
In the case of kind, the coarse powder obtained at the end of this method does not contain metallic compound residue yet, therefore does not have color change,
And it is complete no problem from the perspective of food.
Brief description of the drawings
Advantages and features of the invention will become apparent from from the description of the embodiment of following description starch cationization method
Ground present, provide this method hereinafter with reference to Fig. 1 in accompanying drawing and the device shown in Fig. 2, be purely example by way of
This method is provided.
It is described in detail
With reference to figure 1, the device for the method according to the invention includes the reaction being substantially made up of cylinder tubular body 1
Device R, it is closed by end plate 2,3 in opposite end and has been coaxially disposed heating mantle (or coolant jacket) 4, and it is intended to allow fluid example
If diathermanous oil by the inwall of main body 1 by be maintained at predetermined temperature.
Tubular body 1 is separately provided for the charging aperture 5,6 of the pulverulent material containing starch and aqueous hydrogen peroxide solution,
And discharging opening 7.
Rotor is pivotably supported inside tubular body 1, the rotor includes axle 8, and the axle 8 is provided with the footpath of blade shape
To prominent element 9, these blades 9 are into being spirally positioned and oriented to centrifuge, and simultaneously towards the transmission of discharging opening 7 containing forming sediment
The wet-milling that the pulverulent material of powder and the stream of aqueous hydrogen peroxide solution and pulverulent material are formed after being mixed with hydrogenperoxide steam generator is simultaneously
Reaction.
Motor M is used for the rotor of 50 to 1500rpm variable velocity operation vane type.
When being discharged from reactor, above-mentioned wet-milling is supplied via the pipeline 11 that the discharging opening 7 with reactor connects and injected
Device device 51.
The main body of injection device 51 has tubulose, and is provided with the import 55 and outlet that wet-milling is received from pipeline 11
57。
Blade or screw rotor 58 are pivotably supported inside tubular body 51, it gives wet-milling towards before exporting 57
Enter thrust, wet-milling is transferred to second reactor R' charging aperture 105 by it.It is not described in having and above-mentioned first reactor
The second reactor R' of on all four structure.With the part identical accompanying drawing mark of first reactor identical second reactor
Note represents plus 100.Only refer to that charging aperture 106 is used to supply ammonia spirit stream.
The pipeline 111 that the wet-milling exported from discharging opening 107 connects via the discharging opening 107 with second reactor R' is supplied to
Injection device 151.With the part of the identical injection device 151 of injection device 51 100 are added with identical reference
Represent.
By the outlet 157 of injection device 151, wet-milling is discharged and supplies turbo dryer T. by charging aperture 205
Turbo dryer T is substantially made up of cylinder tubular body 201, and it passes through end plate 202,203 envelopes in opposite end
Close and be coaxially disposed heating mantle (or coolant jacket) 204, it is intended to allow for example diathermanous oil of fluid by so as to by main body 201
Inwall be maintained at predetermined temperature.
Tubular body 201 be provided with for introduce the wet-milling discharged by injection device 151 and hot-air opening 205,
206, and discharging opening 7.
Rotor is pivotably supported inside tubular body 201, the rotor includes axle 108, and the axle 108 is provided with blade-shaped
The radially projecting element 209 of formula, these blades 209 are into being spirally positioned and oriented to centrifuge, while towards discharging
Mouth 207 transmits hot-airs and wet-milling.Discharging opening 207 is used to discharge the continuous stream of hot-air and water vapour and contains oxidized starch
Pulverulent material, the pulverulent material containing oxidized starch is pulverulent material and the wall of turbo dryer that is heated by heating mantle 204
Dry what above-mentioned wet-milling obtained with stream of hot air after heat exchange.
The stream and water vapour of pulverulent material and hot-air containing oxidized starch are finally transported to container 18, for receiving
Collection and separation are also from the steam and air of turbo dryer discharge.
With reference to figure 2, for the device of the method according to the invention, in its alternative embodiment, including substantially by
The first reactor R " that cylinder tubular body 301 forms, it is closed and is coaxially disposed by end plate 302,303 in opposite end
There is heating mantle (or coolant jacket) 304, it is intended to allow for example diathermanous oil of fluid by so as to which the inwall of main body 301 is maintained at into pre-
Constant temperature degree.
Tubular body 301 is separately provided for the charging aperture of the pulverulent material containing starch and aqueous hydrogen peroxide solution
305th, 306, it is arranged near end plate 302, for the charging aperture 310 of ammonia spirit, roughly equidistant in end plate 302 and 303
Position arranged along tubular body 301, and discharging opening 307.
Rotor is pivotably supported inside tubular body 301, the rotor includes axle 308, and the axle 308 is provided with blade-shaped
The radially projecting element 309 of formula, these blades 309 are into being spirally positioned and oriented to centrifuge, while towards discharging
Mouth 307 transmits the wet-millings formed after the pulverulent materials containing starch, aqueous hydrogen peroxide solution and ammonia spirit and mixing, and
Pulverulent material is set to be reacted with aqueous hydrogen peroxide solution and ammonia spirit.
Motor M is used for the rotor of 50 to 1500rpm variable velocity operation vane type.
When being discharged from reactor, above-mentioned wet-milling is supplied via the pipeline 311 that the discharging opening 307 with reactor connects and noted
Mapper arrangement 351.
The main body of injection device 351 has tubulose, and is provided with the import 355 that wet-milling is received from pipeline 311, and
Outlet 357.
The device also include with the above-mentioned on all four turbo dryer T' of the turbo dryer T further described, therefore
It is not described in detail.Part with the above-mentioned turbodrier identical turbodrier T' further described is by identical accompanying drawing mark
Note represents plus 200.
The device finally includes being used for what is collected the pulverulent material containing oxidized starch and separate it with steam and air
Container 18, wherein steam and air also export from turbo dryer.
Embodiment 1
The farina stream for the powdery that water content is 20% is continuously supplied into (100kg/h) reactor R by opening 6,
Wherein blade rotor 8 is rotated with 700rpm speed.Meanwhile the hydrogen peroxide of equivalent to about 10.9%w/v 36 volumes is water-soluble
Liquid stream passes through the continuous feed of opening 5 (10l/h).
The temperature of inwall is maintained at about 20 DEG C.
At reactor R charging aperture, starch flow is mechanically dispersed into particle immediately, and it is centrifuged immediately and leans against reaction
On the inwall of device, wherein forming dynamic, tubulose, thin fluid layer.Meanwhile the aqueous hydrogen peroxide solution quilt supplied by opening 5
The blade atomization of rotor 8 is fine, and the blade of rotor 8 is also centrifuged immediately to the superfine drop of acquisition.Therefore, the latter is drawn
Enter dynamic, tubulose, thin starch granules fluid layer in, thus make that between them close interaction can be produced.
Mean residence time continuously discharges the powder that water content is 28% from opening 7 after about 30 seconds in reactor.
The wet-milling is by syringe 51 by opening 105 with the continuous supplied reactor R' of 100kg/h flow.
In reactor R', wall temperature is maintained at about 20 DEG C, at the same the rotation speed constant of blade rotor 108 be maintained at
800rpm。
It is 10l/h that the continuous flow-through opening 106 of ammonia spirit (10%w/v) is fed into reactor R'(flows).
After averagely stopping 20 seconds in reactor, the wet-milling that water content is 35% is by opening 107 from the reactor
Continuous discharge.
The wet-milling is continually fed into turbo dryer T by syringe 151 via opening 205 with 100kg/h flow
In, at the same by opening 206 at a temperature of 100 DEG C (flow 500m3/ h) supply air stream.
In turbodrier T inside, wall temperature is maintained at 150 DEG C, while the rotation speed constant of blade rotor 108
Ground is maintained at 1000rpm.
Mean residence time in turbodrier T is after 20 seconds, and the powdery oxidised potato that water content is 10% forms sediment
Powder is continuously discharged from the turbodrier.
The viscosity of 10% aqueous solution of the oxidized starch powder is determined, obtains viscosity number 10cps, wherein starting starch powder
The viscosity of 10% aqueous solution at end is equal to 1450cps.
Oxidized starch powder is completely white and odorless, also without any metallic compound residue, therefore it is completely suitable
For all purposes of oxidized starch, particularly food and medicinal usage.
Embodiment 2
The cornstarch stream for the powdery that water content is 18% is continuously supplied into (80kg/h) reactor R " by opening 306,
Wherein blade rotor 308 is rotated with 800rpm speed.Meanwhile equivalent to about 9.1%w/v hydrogenperoxide steam generator stream is by opening
305 continuous feeds of mouth (10l/h), and the continuous feed of ammonia spirit continuous flow-through import 310 of 9%w/v 30 volumes
(10l/h).The temperature of inwall is maintained at about 20 DEG C.
Mean residence time continuously discharges the powder that water content is 33% from opening 307 after about 30 seconds in reactor.
The wet-milling is continuously supplied into turbo dryer T' by syringe 351 via opening 405 with 80kg/h flow, together
When by opening 406 at a temperature of 100 DEG C (flow 400m3/ h) supply air stream.
In turbo dryer T', wall temperature is maintained at 150 DEG C, at the same the rotation speed constant of blade rotor 108 protect
Hold in 1000rpm.
Mean residence time in turbodrier T' is after 20 seconds, and water content is 10% powdery oxidised maize starch
Continuously discharged from the turbodrier.
The viscosity of 10% aqueous solution of the oxidized starch powder is determined, obtains viscosity number 11cps, wherein starting starch powder
The viscosity of 10% aqueous solution at end is equal to 1410cps.
Oxidized starch powder is completely white and odorless, also without any metallic compound residue, therefore it is completely suitable
For all purposes of oxidized starch, particularly food and medicinal usage.
Embodiment 3
The O-shaped wheat flour that water content is 14% is continuously supplied into (100kg/h) reactor R by opening 6, wherein blade turns
Son 8 is rotated with 900rpm speed.Meanwhile the aqueous hydrogen peroxide solution stream of equivalent to about 10.9%w/v 36 volumes is by opening
5 continuous feeds of mouth (10l/h).The temperature of inwall is maintained at about 20 DEG C.
Mean residence time continuously discharges the powder that water content is 27% from opening 7 after about 30 seconds in reactor.
The wet-milling is by syringe 51 by opening 105 with the continuous supplied reactor R' of 100kg/h flow.
In reactor R', wall temperature is maintained at about 20 DEG C, at the same the rotation speed constant of blade rotor 108 be maintained at
800rpm。
It is 10l/h that the continuous flow-through opening 106 of ammonia spirit (10%w/v) is fed into reactor R'(flows).
After averagely stopping 20 seconds in reactor, the wet-milling that water content is 34% is by opening 107 from the reactor
Continuous discharge.
The wet-milling is continuously supplied into turbo dryer T by syringe 151 via opening 205 with 100kg/h flow, together
When by opening 206 at a temperature of 100 DEG C (flow 500m3/ h) supply air stream.
In turbo dryer T, wall temperature is maintained at 150 DEG C, at the same the rotation speed constant of blade rotor 108 keep
In 900rpm.
Mean residence time in turbodrier T is after 20 seconds, water content for 13% powdery oxidized starch from institute
State in turbodrier and continuously discharge.
Resulting flour is white and odorless, also no any metallic compound residue, therefore be wholly adapted to
People eats.
The gliadin of flour contacts as obtained by electrophoresis (SDS-PAGE) measure on polyacrylamide gel
(gliadin contact), causes to be substantially absent from gliadin, and this shows that the method according to the invention causes in flour
Contained gliadin it is degradable.
Therefore, this flour is eaten particularly suitable for the people not tolerated with celiaca or seitan.
Claims (26)
1. a kind of method for being used to aoxidize the pulverulent material containing starch, wherein, methods described is in the absence of any metallization
It is being carried out in the case of compound and including following step one by one：
A) pulverulent material containing starch is provided；
B) by the pulverulent material and aqueous hydrogen peroxide solution (H2O2) mixing；And
C) ammonia spirit is added into thus obtained mixture and it is reacted with the mixture.
2. the step of according to the method for claim 1, in addition to the mixture of the step c) being dried, to obtain
Pulverulent material containing oxidized starch.
3. according to the method for claim 2, wherein, the pulverulent material containing starch is selected from the starch by separate sources
The group of composition, especially from corn, potato, wheat, cassava, rice and the starch of beans, the coarse powder from cereal, wherein
Cereal particularly wheat, rice, corn, barley, rye, oat, buckwheat, three-coloured amaranth and quinoa；And the coarse powder from beans, its
Middle beans particularly beans, pea, chick-pea, broad bean, French beans, lupin, chickling and soybean.
4. according to the method any one of claim 2 and 3, wherein, the w/v concentration of the aqueous hydrogen peroxide solution is Jie
Between 5% to 20%.
5. according to the method for claim 4, wherein, the w/v concentration of the ammonia spirit is between 5% to 20%.
6. according to the method any one of claim 2-5, wherein, the pulverulent material containing starch and the peroxide
Change the weight ratio between aqueous solution of hydrogen between 3 to 20.
7. the method according to claim 11, wherein, the weight between the aqueous hydrogen peroxide solution and the ammonia spirit
Than generally between 1 to 10.
8. according to the method any one of claim 2-7, wherein, made by the drying steps described containing oxidation shallow lake
The water content of the pulverulent material of powder is less than or 20 weights of gross weight equal to the pulverulent material containing oxidized starch
Measure %, preferably 5 to 15 weight %.
9. a kind of method for aoxidizing the pulverulent material according to claim 2 containing starch, this method comprise the following steps：
A) first reactor (R) is provided, it includes the cylinder tubular body (1) with horizontal axis, and it has at least one use
In the opening (5,6) and at least one opening (7) for being used to discharge final products that introduce reagent；And optionally with described in making
The temperature of tubular body reaches the heating mantle or coolant jacket (4) of predetermined temperature；And rotor, it is arranged in cylinder tubular body
And the axle (8) of prominent element (9) is radially therefrom including being provided with, and the continuous stream of the pulverulent material containing starch is supplied
The first reactor, wherein rotor are rotated with the speed more than or equal to 50rpm, by the pulverulent material containing starch
Continuous stream be dispersed into the particle stream of the material；
B) continuous stream of aqueous hydrogen peroxide solution supplies the reaction together with the continuous stream of the pulverulent material containing starch
Device, the continuous stream of the aqueous hydrogen peroxide solution are dispersed into fine droplet stream by the rotor；
C) particle and drop centrifugation are leaned against into the first reactor (R) inwall, formed high turbulence, dynamic,
Thin tubular fluid layer, wherein the drop of the particle of the pulverulent material containing starch and the aqueous hydrogen peroxide solution pass through it is described
The radially projecting element (9) of rotor keeps mechanically being in close contact, while with the inwall with reactor substantially contiguously
Promoted towards discharging opening (7)；
D) when promoting the inwall for generally contacting turbo-reactor towards discharging opening (7), the pulverulent material containing starch
Reacted with hydrogen peroxide in the thin layer；
E) second reactor (R') is supplied from the continuous stream of the discharging opening (7) discharge wet-milling and by the continuous stream, described the
Two reactors include the cylinder tubular body (101) with horizontal axis, and it is provided with least one for introducing opening for reagent
Mouth (105,106) and at least one opening (107) for being used to discharge final products；Optionally with the temperature for making the tubular body
Degree reaches the heating mantle or coolant jacket (104) of predetermined temperature；And rotor (8), its be arranged in cylinder tubular body and including
The axle (108) for being radially therefrom prominent element (109) is provided with, wherein rotor is rotated with the speed more than or equal to 50rpm；
F) continuous stream of ammonia spirit supplies the second reactor, the continuous stream of the ammonia spirit together with the wet-milling stream
Fine droplet stream is dispersed into by the rotor；
G) continuous flow centrifugation is made to lean against described second by the action of the radially projecting element (109) of the rotor
The inwall of reactor (R') so that they are contacted towards discharging opening (107) substantially with the inwall with the second reactor
It is mobile；
H) from the continuous stream of wet-milling of the discharging opening (107) discharge containing oxidized starch；
I) the wet-milling drying to water content is less than or equal to 20 weight %, so as to obtain the powdery material containing oxidized starch
Material.
10. a kind of method for aoxidizing the pulverulent material containing starch, this method comprise the following steps：
A' reactor (R ")) is provided, it includes the cylinder tubular body (301) with horizontal axis, is provided with described in being arranged in
The first opening (306) and the second opening (305) that are used to introduce reagent of the adjacent one end of cylinder tubular body, are disposed in
Position between the opposite end of the first end of the cylinder tubular body and the cylinder tubular body is used to introduce reagent
The 3rd opening (310), it is at least one to be used to discharge the openings (307) of final products；Optionally with making the tubular body
Temperature reach the heating mantle or coolant jacket (304) of predetermined temperature；And rotor, its be arranged in cylinder tubular body and including
The axle (308) for being radially therefrom prominent element (309) is provided with, and starch will be contained by the first charging aperture (306)
The continuous stream of pulverulent material supply the reactor (R "), rotor is rotated with the speed more than or equal to 50rpm, will described in
The continuous stream of pulverulent material containing starch is dispersed into the particle stream of the material；
B' the continuous stream of aqueous hydrogen peroxide solution) is supplied by the reactor, the peroxide by the second charging aperture (305)
The continuous stream for changing aqueous solution of hydrogen is dispersed into fine droplet stream by the rotor；
C' the particle and drop centrifugation) are leaned against into the inwall of the reactor (R "), form high turbulence, dynamic, thin
Tubular fluid layer, wherein the drop of the particle of the pulverulent material containing starch and the aqueous hydrogen peroxide solution passes through described turn
The radially projecting element of son keeps mechanically being in close contact, while contiguously direction goes out substantially with the inwall with reactor
Material mouth promotes；
D') when promoting the generally inwall of contact reactor towards discharging opening (307), the pulverulent material containing starch is made
Interacted with hydrogen peroxide in the thin layer；
E' the continuous stream of ammonia spirit) is supplied by the reactor by the 3rd charging aperture (310), the ammonia spirit
Continuous stream is dispersed into fine droplet stream by above-mentioned rotor；
F') to lean against the continuous flow centrifugation by the action of the radially projecting element (309) of the rotor described anti-
Answer the inwall of device so that they are contiguously moved towards discharging opening substantially with the inwall with the reactor；
G') from the continuous stream of wet-milling of the discharging opening discharge containing oxidized starch；
H' the wet-milling drying to water content) is less than or equal to 20 weight %, so as to obtain the powdery material containing oxidized starch
Material.
11. the method according to claim 9 or 10, wherein, step is dried by turbo dryer (T, T') respectively
I) and h'), the turbo dryer (T, T') include with horizontal axis cylinder tubular body (201,401), it is provided with
At least one charging aperture (205,206,405,406) and at least one discharging opening (207,407)；For making the tubular body
Temperature reaches the heating mantle (204,404) of predetermined temperature；And rotor, its be arranged in cylinder tubular body and including with from
The axle (208,408) of its radially projecting element (209,409),
- by least one charging aperture (205,405), it will be sent into from the wet-milling that the reactor (R', R ") is discharged
In the turbo dryer (T, T'), the inwall of turbo dryer is maintained at least 70 DEG C of temperature by the heating mantle, and
And rotor is rotated with least 150rpm speed；
- centrifuge and the wet-milling is promoted by the action of the rotor in turbo dryer；And
- formed sediment from discharging opening (207, the 407) discharge of turbo dryer with water content less than or equal to 20 weight % containing oxidation
The continuous stream of the pulverulent material of powder.
12. the method according to claim 11, wherein, with the wet-milling is streamed into the same of turbo dryer (T, T')
When, the gas stream for being heated at least 50 DEG C of temperature is also fed to the whirlpool by least one charging aperture (206,406)
Take turns in drier, wherein the gas stream is preferably air stream.
13. according to the method for claim 12, wherein, the temperature of the inwall of the turbo dryer (T, T') is maintained at
70-180 DEG C, preferably 130-150 DEG C, and the temperature for being sent into the air-flow of turbo dryer is preferably between 50 DEG C to 250 DEG C, closes
Preferably between 120 DEG C to 150 DEG C.
14. the method according to any one of claim 9 to 13, wherein, the institute protruded from the Axial and radial of the rotor
State the form that element (9,109,209,409) is bar, blade, V-arrangement blade or agitator.
15. according to the method described in any one of claim 9-14, wherein, the w/v concentration of the aqueous hydrogen peroxide solution
For between 5% to 20%.
16. according to the method for claim 15, wherein, the w/v concentration of the ammonia spirit be between 5% to 20% it
Between.
17. according to the method described in any one of claim 9-16, wherein, the flow of the aqueous hydrogen peroxide solution stream with
Ratio between the flow of the pulverulent material stream containing starch is between 1:20 to 1:Between 5,1 is preferably ranges between:15 to
1:Between 8.
18. the method according to claim 11, wherein, the flow of the ammonia spirit stream and the powdery containing starch
Ratio between the flow of material stream is between 1:20 to 1:Between 5,1 is preferably ranges between:15 to 1:Between 8.
19. according to the method described in any one of claim 9-18, wherein, made by the drying steps described containing aerobic
Change starch pulverulent material water content be less than or equal to the pulverulent material containing oxidized starch gross weight 5 to
15 weight %.
20. a kind of be used to implement the equipment for aoxidizing the method for the pulverulent material containing starch according to claim 9, it is wrapped
Include：
First reactor (R), including the cylinder tubular body (1) with horizontal axis, it has at least one for introducing examination
The opening (5,6) of agent and at least one opening (7) for being used to discharge final products；Optionally with the temperature for making the tubular body
Degree reaches the heating mantle or coolant jacket (4) of predetermined temperature；And rotor, it is arranged in cylinder tubular body and including being provided with
It is radially therefrom the axle (8) of prominent element (9)；
Second reactor (R'), including the cylinder tubular body (101) with horizontal axis, it has at least one for introducing
The opening (105,106) of reagent and at least one opening (107) for being used to discharge final products；Optionally with making the tubulose
The temperature of main body reaches the heating mantle or coolant jacket (104) of predetermined temperature；And rotor, it is arranged in cylinder tubular body simultaneously
The axle (108) of prominent element (109) is radially therefrom including being provided with.
21. a kind of be used to implement the equipment for aoxidizing the method for the pulverulent material containing starch according to claim 10, it is wrapped
Include：
Reactor (R "), it includes the cylinder tubular body (301) with horizontal axis, and it, which is provided with, is arranged in the cylindrical duct
The first opening (306) and the second opening (305) that are used to introduce reagent of the adjacent one end of shape main body, are disposed in the circle
Position between the cylinder first end of tubular body and the opposite end of the cylinder tubular body is used to introduce the 3rd of reagent
It is open (310), at least one opening (307) for being used to discharge final products；Optionally with the temperature for making the tubular body
Reach the heating mantle or coolant jacket (304) of predetermined temperature；And rotor, it is arranged in cylinder tubular body and including being provided with
It is radially therefrom the axle (308) of prominent element (309).
22. equipment according to claim 20, further comprising turbo dryer (T), it is included with horizontal axis
Cylinder tubular body (201), there is at least one charging aperture (205,206) and at least one discharging opening (207)；Heating mantle
(204)；And rotor, it is arranged in cylinder tubular body and the axle of prominent element (209) is radially therefrom including being provided with
(208)。
23. equipment according to claim 21, further comprising turbo dryer (T'), it is included with horizontal axis
Cylinder tubular body (401), there is at least one charging aperture (405,406) and at least one discharging opening (407)；Heating mantle
(404)；And rotor, it is arranged in cylinder tubular body and the axle of prominent element (409) is radially therefrom including being provided with
(408)。
24. equipment according to claim 22, further comprises：
Injection device (51) with tubular body, it is provided with import (7), and at least one with the first reactor (R)
Individual discharging opening (7) fluidly connects, and outlet (57), is flowed with least one charging aperture (105) of the second reactor (R')
Body connects；The blade or screw rotor (58) being supported in the tubular body；And
Injection device (151) with tubular body, it is provided with import (155), with the second reactor (R') extremely
A few discharging opening (107) fluidly connects, and outlet (157), at least one charging aperture with turbo dryer (R')
(205) fluidly connect；The blade or screw rotor (158) being supported in the tubular body.
25. equipment according to claim 23, further comprise the injection device (351) with tubular body, it sets
Import (355) is equipped with, is fluidly connected with least one discharging opening (307) of the reactor (R "), and outlet (357), with
At least one charging aperture (405) of the turbo dryer (T ") fluidly connects；The blade being supported in the tubular body
Or screw rotor (358).
26. a kind of pulverulent material containing oxidized starch, it can pass through the side according to any one of claim 2-19
Method by selected from by including：From corn, potato, wheat, cassava, rice and the starch of beans, from such as wheat, rice,
Corn, barley, rye, oat, buckwheat, three-coloured amaranth and quinoa cereal coarse powder, and come soya bean, pea, chick-pea, silkworm freely
Beans, French beans, lupin, chickling and the coarse powder of the beans of soybean be grouped in pulverulent material and obtain.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI20150457 | 2015-03-30 | ||
| ITMI2015A000457(102015902341457) | 2015-03-30 | ||
| PCT/EP2016/055231 WO2016156009A1 (en) | 2015-03-30 | 2016-03-11 | Process for the oxidation of starch-based materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107667122A true CN107667122A (en) | 2018-02-06 |
Family
ID=53189940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680031137.0A Pending CN107667122A (en) | 2015-03-30 | 2016-03-11 | The method for aoxidizing the material based on starch |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US11732057B2 (en) |
| EP (1) | EP3277729B1 (en) |
| CN (1) | CN107667122A (en) |
| RU (1) | RU2710565C2 (en) |
| WO (1) | WO2016156009A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113597406A (en) * | 2018-12-21 | 2021-11-02 | 涡龙设备与工艺公司 | Method for recovering phosphorus |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT201700073160A1 (en) * | 2017-06-29 | 2018-12-29 | Ambiente E Nutrizione Srl | Process for the production of thermally modified starch |
| SE541492C2 (en) * | 2017-08-11 | 2019-10-15 | Lyckeby Starch Ab | Method for preparing an inhibited starch |
| CN114031692B (en) * | 2020-08-04 | 2023-03-31 | 山东福洋生物科技股份有限公司 | Method for reducing COD (chemical oxygen demand) of wastewater in oxidized starch preparation process |
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Also Published As
| Publication number | Publication date |
|---|---|
| RU2017133825A3 (en) | 2019-07-24 |
| RU2710565C2 (en) | 2019-12-27 |
| US20180112012A1 (en) | 2018-04-26 |
| WO2016156009A1 (en) | 2016-10-06 |
| RU2017133825A (en) | 2019-04-30 |
| EP3277729A1 (en) | 2018-02-07 |
| EP3277729B1 (en) | 2019-05-01 |
| US11732057B2 (en) | 2023-08-22 |
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